U.S. patent application number 10/670388 was filed with the patent office on 2004-06-24 for nail varnish composition comprising a block polymer.
Invention is credited to Leuridan, Frederic, Lion, Bertrand, Toumi, Beatrice.
Application Number | 20040120906 10/670388 |
Document ID | / |
Family ID | 32045662 |
Filed Date | 2004-06-24 |
United States Patent
Application |
20040120906 |
Kind Code |
A1 |
Toumi, Beatrice ; et
al. |
June 24, 2004 |
Nail varnish composition comprising a block polymer
Abstract
The present invention relates to a nail varnish composition
comprising, in a cosmetically acceptable medium comprising at least
one organic solvent, at least one block polymer, the composition
being capable of forming a film with a tangent delta (tg.delta.)
dampening power of greater than or equal to 0.4 at a temperature of
30.degree. C. and a frequency of 20 Hz. A further subject of the
invention is a method for producing a glossy film comprising
applying to nails such a composition, wherein a glossy film is
produced and which shows good staying power and/or wear
resistance.
Inventors: |
Toumi, Beatrice; (Verrieres
le Buisson, FR) ; Lion, Bertrand; (Luzarches, FR)
; Leuridan, Frederic; (Paris, FR) |
Correspondence
Address: |
Thomas L. Irving
FINNEGAN, HENDERSON, FARABOW,
GARRETT & DUNNER, L.L.P.
1300 I Street , N.W.
Washington
DC
20005-3315
US
|
Family ID: |
32045662 |
Appl. No.: |
10/670388 |
Filed: |
September 26, 2003 |
Current U.S.
Class: |
424/61 |
Current CPC
Class: |
C08L 53/00 20130101;
A61K 8/26 20130101; A61K 8/8111 20130101; Y10S 514/844 20130101;
A61K 8/8182 20130101; C08F 293/005 20130101; A61Q 1/10 20130101;
Y10S 514/845 20130101; C08L 51/003 20130101; Y10S 514/937 20130101;
A61Q 1/04 20130101; C08F 265/06 20130101; A61K 8/922 20130101; C08L
53/00 20130101; A61K 2800/594 20130101; A61Q 1/06 20130101; A61Q
3/02 20130101; C08F 265/04 20130101; A61K 8/891 20130101; A61K
8/927 20130101; A61K 8/90 20130101; C08F 291/00 20130101; A61K
8/8152 20130101; C08L 51/003 20130101; C08L 2666/02 20130101; C08L
2666/02 20130101 |
Class at
Publication: |
424/061 |
International
Class: |
A61K 007/04 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 26, 2002 |
FR |
02 11949 |
Dec 20, 2002 |
FR |
02 16437 |
May 21, 2003 |
FR |
03 06121 |
Claims
What is claimed is:
1. A nail varnish composition comprising, in a cosmetically
acceptable medium comprising at least one organic solvent, at least
one block polymer, the composition being capable of forming a film
with a dampening power (tg.delta.) of greater than or equal to 0.4
at a temperature of 30.degree. C. and a frequency of 20 Hz.
2. The composition according to claim 1, wherein the dampening
power of the film is greater than or equal to 0.5.
3. The composition according to claim 1, wherein the film of the
composition has a storage modulus E' of greater than or equal to 1
MPa, at a temperature of 30.degree. C. and a frequency of 0.1
Hz.
4. The composition according to claim 3, wherein the storage
modulus E' of the film is greater than or equal to 5 MPa.
5. The composition according to claim 4, wherein the storage
modulus E' of the film is greater than or equal to 10 Mpa.
6. The composition according to claim 1, wherein the film of the
composition has a breaking strain .delta.r of greater than or equal
to 5%, and/or a breaking energy per unit volume Wr of greater than
or equal to 0.2 J/cm.sup.3 at a temperature of 20.degree. C.
7. The composition according to claim 6, wherein the film has a
breaking strain .delta.r ranging from 5% to 500% and/or a breaking
energy per unit volume Wr of greater than or equal to 0.2
J/cm.sup.3 at a temperature of 20.degree. C.
8. The composition according to claim 7, wherein the film has a
breaking strain .delta.r greater than or equal to 15% and/or a
breaking energy per unit volume Wr of greater than or equal to 0.2
J/cm.sup.3 at a temperature of 20.degree. C.
9. The composition according to claim 8, wherein the film has a
breaking strain .delta.r ranging from 15% to 400% and/or a breaking
energy per unit volume Wr of greater than or equal to 0.2
J/cm.sup.3 at a temperature of 20.degree. C.
10. The composition according to claim 1, wherein the at least one
block polymer comprises at least a first block and at least a
second block that have different glass transition temperatures
(Tg), wherein the at least one first and second blocks are linked
together via at least one intermediate segment comprising at least
one constituent monomer of the at least one first block and at
least one constituent monomer of the at least one second block.
11. The composition according to claim 10, wherein said at least
one first block and said at least one second block are incompatible
with each other.
12. The composition according to claim 10, wherein the at least one
first block is chosen from: a) a block with a Tg of greater than or
equal to 40.degree. C., b) a block with a Tg of less than or equal
to 20.degree. C., c) a block with a Tg of between 20 and 40.degree.
C., and wherein the at least one second block is chosen from a
block of category a), b) or c) that is different from the at least
one first block.
13. The composition according to claim 12, wherein the block with a
Tg of greater than or equal to 40.degree. C. is totally or
partially derived from at least one monomer wherein a homopolymer
prepared from the at least one monomer has a Tg of greater than or
equal to 40.degree. C.
14. The composition according to claim 13, wherein the at least one
monomer is chosen from: methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)- --COOR.sub.1 wherein R.sub.1 is chosen
from linear and branched unsubstituted alkyl groups comprising from
1 to 4 carbon atoms, and from a C.sub.4 to C.sub.12 cycloalkyl
group, acrylates of formula CH.sub.2.dbd.CH--COOR.sub.2 wherein
R.sub.2 is chosen from a C.sub.4 to C.sub.12 cycloalkyl group, and
(meth)acrylamides of formula: 2wherein R.sub.7 and R.sub.8, which
may be identical or different, each are chosen from a hydrogen
atom, and linear or branched alkyl groups comprising 1 to 12 carbon
atoms; or R.sub.7 is H and R.sub.8 is a 1,1-dimethyl-3-oxobutyl
group, and R' is chosen from H and methyl.
15. The composition according to claim 14, wherein the
unsubstituted alkyl group of R.sub.1 is chosen from a methyl, an
ethyl, a propyl, and an isobutyl group.
16. The composition according to claim 14, wherein the C.sub.4 to
C.sub.12 cycloalkyl group of R.sub.2 is chosen from an isobornyl
group and a tert-butyl group.
17. The composition according to claim 14, wherein the alkyl group
with 1 to 12 carbon atoms of R.sub.7 and R.sub.8 is chosen from an
n-butyl, a t-butyl, an isopropyl, an isohexyl, an isooctyl, and an
isononyl group.
18. The composition according to claim 13, wherein the at least one
monomer is chosen from methyl methacrylate, isobutyl methacrylate,
and isobornyl (meth)acrylate.
19. The composition according to claim 12, wherein the block with a
Tg of less than or equal to 20.degree. C. is totally or partially
derived from at least one monomer wherein a homopolymer prepared
from the at least one monomer has a Tg of less than or equal to
20.degree. C.
20. The composition according to claim 19, wherein the at least one
monomer is chosen from: acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, wherein R.sub.3 is chosen from linear
and branched C.sub.1 to C.sub.12 unsubstituted alkyl groups, with
the exception of a tert-butyl group, wherein at least one
heteroatom chosen from O, N and S is optionally intercalated;
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub- .4,
wherein R.sub.4 is chosen from linear and branched C.sub.6 to
C.sub.12 unsubstituted alkyl groups, wherein at least one
heteroatom chosen from O, N and S is optionally intercalated; vinyl
esters of formula R.sub.5--CO--O--CH.dbd.CH.sub.2 wherein R.sub.5
is chosen from linear and branched C.sub.4 to C.sub.12 alkyl
groups; C.sub.4 to C.sub.12 alcohol and vinyl alcohol ethers; and
N--(C.sub.4 to C.sub.12)alkyl acrylamides.
21. The composition according to claim 20, wherein said N--(C.sub.4
to C.sub.12)alkyl acrylamide is N-octylacrylamide.
22. The composition according to claim 20, wherein the at least one
monomer is chosen from alkyl acrylates whose alkyl chain contains
from 1 to 10 carbon atoms, with the exception of the tert-butyl
group.
23. The composition according to claim 12, wherein the block with a
Tg of between 20 and 40.degree. C. is totally or partially derived
from at least one monomer wherein a homopolymer prepared from the
at least one monomer has a Tg of between 20 and 40.degree. C.
24. The composition according to claim 23, wherein the block with a
Tg of between 20 and 40.degree. C. is totally or partially derived
from at least one monomer wherein the corresponding homopolymer has
a Tg of greater than or equal to 40.degree. C. and from at least
one monomer wherein the corresponding homopolymer has a Tg of less
than or equal to 20.degree. C.
25. The composition according to claim 23, wherein the block with a
Tg of between 20 and 40.degree. C. is totally or partially derived
from at least one monomer chosen from methyl methacrylate,
isobornyl acrylate, isobornyl methacrylate, trifluoroethyl
methacrylate, butyl acrylate, and 2-ethylhexyl acrylate.
26. The composition according to claim 1, wherein the at least one
block polymer comprises at least one first block and at least one
second block, the at least one first block having a Tg of greater
than or equal to 40.degree. C., and the at least one second block
having a Tg of less than or equal to 20.degree. C., the at least
one first and second blocks are linked together via at least one
intermediate segment comprising: at least one constituent monomer
of the at least one first block and at least one constituent
monomer of the at least one second block.
27. The composition according to claim 26, wherein the at least one
first block is totally or partially derived from at least one
monomer wherein a homopolymer prepared from the at least one
monomer has a Tg of greater than or equal to 40.degree. C.
28. The composition according to claim 26, wherein the at least one
first block is a copolymer derived from at least one monomer
wherein the homopolymer prepared from the at least one monomer has
a Tg of greater than or equal to 40.degree. C.
29. The composition according to claim 27, wherein the at least one
monomer is chosen from: methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)- --COOR.sub.1 wherein R.sub.1 is chosen
from linear and branched unsubstituted alkyl groups containing from
1 to 4 carbon atoms, and from a C.sub.4 to C.sub.12 cycloalkyl
group, acrylates of formula CH.sub.2.dbd.CH--COOR.sub.2 wherein
R.sub.2 is a C.sub.4 to C.sub.12 cycloalkyl group, and
(meth)acrylamides of formula: 3wherein R.sub.7 and R.sub.8, which
may be identical or different, each are chosen from a hydrogen
atom, linear and branched alkyl groups comprising 1 to 12 carbon
atoms; or R.sub.7 is H and R.sub.8 is a 1,1-dimethyl-3-oxobutyl
group, and R' is chosen from H and methyl.
30. The composition according to claim 29, wherein the
unsubstituted alkyl group of R.sub.1 is chosen from a methyl, an
ethyl, a propyl, and an isobutyl group.
31. The composition according to claim 29, wherein the C.sub.4 to
C.sub.12 cycloalkyl group of R.sub.2 is chosen from an isobornyl
group and a tert-butyl group.
32. The composition according to claim 29, wherein the alkyl group
with 1 to 12 carbon atoms of R.sub.7 and R.sub.8 is chosen from an
n-butyl, a t-butyl, an isopropyl, an isohexyl, an isooctyl, and an
isononyl group.
33. The composition according to claim 27, wherein the at least one
monomer is chosen from methyl methacrylate, isobutyl methacrylate,
and isobornyl (meth)acrylate.
34. The composition according to claim 26, wherein the at least one
first block is present in the at least one block polymer in an
amount ranging from 20% to 90% by weight of the at least one block
polymer.
35. The composition according to claim 34, wherein at least one
first block is present in the at least one block polymer in an
amount ranging from 30% to 80% by weight of the at least one block
polymer.
36. The composition according to claim 35, wherein the at least one
first block is present in the at least one block polymer in an
amount ranging from 50% to 70% by weight of the polymer
37. The composition according to claim 26, wherein the at least one
second block is totally or partially derived from at least one
monomer wherein a homopolymer prepared from the at least one
monomer has a Tg of less than or equal to 20.degree. C.
38. The composition according to claim 26, wherein the at least one
second block is a homopolymer derived from at least one monomer
wherein a homopolymer prepared from the at least one monomer has a
Tg of less than or equal to 20.degree. C.
39. The composition according to claim 37, wherein the at least one
monomer is chosen from: acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, wherein R.sub.3 is chosen from linear
and branched C.sub.1 to C.sub.12 unsubstituted alkyl groups, with
the exception of the tert-butyl group, wherein at least one
heteroatom chosen from O, N and S is optionally intercalated;
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub- .4,
wherein R.sub.4 is chosen from linear and branched C.sub.6 to
C.sub.12 unsubstituted alkyl groups, wherein at least one
heteroatom chosen from O, N and S is optionally intercalated; vinyl
esters of formula R.sub.5--CO--O--CH.dbd.CH.sub.2 wherein R.sub.5
is chosen from linear and branched C.sub.4 to C.sub.12 alkyl
groups; C.sub.4 to C.sub.12 alcohol and vinyl alcohol ethers; and
N--(C.sub.4 to C.sub.12)alkyl acrylamides.
40. The composition according to claim 39, wherein the N--(C.sub.4
to C.sub.12)alkyl acrylamide is N-octylacrylamide.
41. The composition according to claim 37, wherein the at least one
monomer is chosen from alkyl acrylates whose alkyl chain contains
from 1 to 10 carbon atoms, with the exception of the tert-butyl
group.
42. The composition according to claim 26, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 5% to 75% by weight of the at least one block
polymer.
43. The composition according to claim 42, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 15% to 50% by weight of the at least one block
polymer.
44. The composition according to claim 43, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 25% to 45% by weight of the at least one block
polymer.
45. The composition according to claim 1, wherein the at least one
block polymer comprises at least one first block and at least one
second block, the at least one first block having a Tg of between
20 and 40.degree. C. and the at least one second block having a Tg
of less than or equal to 20.degree. C. or a Tg of greater than or
equal to 40.degree. C., wherein the at least one first and second
blocks are linked together via at least one intermediate segment
comprising at least one constituent monomer of the at least one
first block and at least one constituent monomer of the at least
one second block.
46. The composition according to claim 45, wherein the at least one
first block is totally or partially derived from at least one
monomer wherein a homopolymer prepared from the at least one
monomer has a Tg of between 20 and 40.degree. C.
47. The composition according to claim 45, wherein the at least one
first block is a copolymer derived from at least one monomer
wherein a corresponding homopolymer has a Tg of greater than or
equal to 40.degree. C., and from at least one monomer wherein a
corresponding homopolymer has a Tg of less than or equal to
20.degree. C.
48. The composition according to claim 45, wherein the at least one
first block is derived from at least one monomer chosen from methyl
methacrylate, isobornyl acrylate, isobornyl methacrylate, butyl
acrylate, and 2-ethylhexyl acrylate.
49. The composition according to claim 45, wherein the at least one
first block of the at least one block polymer is present in an
amount ranging from 10% to 85% by weight of the at least one block
polymer.
50. The composition according to claim 49, wherein the at least one
first block is present in the at least one block polymer in an
amount ranging from 30% to 80% by weight of the at least one block
polymer.
51. The composition according to claim 50, wherein the at least one
first block is present in the at least one block polymer in an
amount ranging from 50% to 70% by weight of the at least one block
polymer.
52. The composition according to claim 45, wherein the at least one
second block has a Tg of greater than or equal to 40.degree. C. and
is totally or partially derived from at least one monomer wherein a
homopolymer prepared from the at least one monomer has a Tg of
greater than or equal to 40.degree. C.
53. The composition according to claim 45, wherein the at least one
second block has a Tg of greater than or equal to 40.degree. C. and
is a homopolymer derived from at least one monomer wherein a
homopolymer prepared from the at least one monomer has a Tg of
greater than or equal to 40.degree. C.
54. The composition according to claim 47, wherein the at least one
monomer is chosen from: methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)- --COOR.sub.1 wherein R.sub.1 is chosen
from linear and branched unsubstituted alkyl groups containing from
1 to 4 carbon atoms, and from a C.sub.4 to C.sub.12 cycloalkyl
group, acrylates of formula CH.sub.2.dbd.CH--COOR.sub.2 wherein
R.sub.2 is chosen from a C.sub.4 to C.sub.12 cycloalkyl group, and
(meth)acrylamides of formula: 4wherein R.sub.7 and R.sub.8, which
may be identical or different, each are chosen from a hydrogen
atom, linear and branched alkyl groups comprising 1 to 12 carbon
atoms; or R.sub.7 is H and R.sub.8 is a 1,1-dimethyl-3-oxobutyl
group, and R' is chosen from H and methyl.
55. The composition according to claim 54, wherein the
unsubstituted alkyl group of R.sub.1 is chosen from a methyl, an
ethyl, a propyl, and an isobutyl group.
56. The composition according to claim 54, wherein the C.sub.4 to
C.sub.12 cycloalkyl group of R.sub.2 is chosen from an isobornyl
group and a tert-butyl group.
57. The composition according to claim 54, wherein the alkyl group
with 1 to 12 carbon atoms of R.sub.7 and R.sub.8 is chosen from an
n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, and isononyl
group.
58. The composition according to claim 47, wherein the at least one
monomer is chosen from methyl methacrylate, isobutyl methacrylate,
and isobornyl (meth)acrylate.
59. The composition according to claim 45, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 10% to 85% by weight of the at least one block
polymer.
60. The composition according to claim 59, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 20% to 70% by weight of the at least one block
polymer.
61. The composition according to claim 60, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 30% to 70% by weight of the at least one block
polymer.
62. The composition according to claim 45, wherein the at least one
second block has a Tg of less than or equal to 20.degree. C. and is
totally or partially derived from at least one monomer wherein a
homopolymer prepared from the at least one monomer has a Tg of less
than or equal to 20.degree. C.
63. The composition according to claim 45, wherein the at least one
second block has a Tg of less than or equal to 20.degree. C. and is
a homopolymer derived from at least one monomer wherein a
homopolymer prepared from the at least one monomer has a Tg of less
than or equal to 20.degree. C.
64. The composition according to claim 62, wherein the at least one
monomer is chosen from: acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, wherein R.sub.3 is chosen from linear
and branched C.sub.1 to C.sub.12 unsubstituted alkyl groups, with
the exception of the tert-butyl group, wherein at least one
heteroatom chosen from O, N and S is optionally intercalated;
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub- .4,
wherein R.sub.4 is chosen from linear and branched C.sub.6 to
C.sub.12 unsubstituted alkyl groups, wherein at least one
heteroatom chosen from O, N and S is optionally intercalated; vinyl
esters of formula R.sub.5--CO--O--CH.dbd.CH.sub.2 wherein R.sub.5
is chosen from linear and branched C.sub.4 to C.sub.12 alkyl
groups; C.sub.4 to C.sub.12 alcohol and vinyl alcohol ethers; and
N--(C.sub.4 to C.sub.12)alkyl acrylamides.
65. The composition according to claim 64, wherein the N--(C.sub.4
to C.sub.12)alkyl acrylamide is N-octylacrylamide.
66. The composition according to claim 62, wherein the at least one
monomer is chosen from alkyl acrylates whose alkyl chain contains
from 1 to 10 carbon atoms, with the exception of the tert-butyl
group.
67. The composition according to claim 62, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 20% to 90% by weight of the at least one block
polymer.
68. The composition according to claim 67, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 30% to 80% by weight of the at least one block
polymer.
69. The composition according to claim 68, wherein the at least one
second block is present in the at least one block polymer in an
amount ranging from 50% to 70% by weight of the at least one block
polymer.
70. The composition according to claim 10, wherein the at least one
first block and/or the at least one second block comprises at least
one additional monomer.
71. The composition according to claim 70, wherein the at least one
additional monomer is chosen from hydrophilic monomers and
ethylenically unsaturated monomers comprising at least one silicon
atom.
72. The composition according to claim 70, wherein the at least one
additional monomer is chosen from: ethylenically unsaturated
monomers comprising at least one carboxylic or sulphonic acid
function, methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6 wherein R.sub.6 is chosen from
linear and branched alkyl groups containing from 1 to 4 carbon
atoms, the alkyl group being substituted with at least one
substituent chosen from hydroxyl groups and halogen atoms,
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9,
wherein R.sub.9 is chosen from linear and branched C.sub.6 to
C.sub.12 alkyl groups wherein at least one heteroatom chosen from
O, N and S is optionally intercalated, the alkyl group being
substituted with at least one substituent chosen from hydroxyl
groups and halogen atoms; acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.10, wherein R.sub.10 is chosen from linear
and branched C.sub.1 to C.sub.12 alkyl groups substituted with at
least one substituent chosen from hydroxyl groups and halogen
atoms, --(C.sub.1-C.sub.12)alkyl-O-POE (polyoxyethylene) with
repetition of the oxyethylene unit from 5 to 30 times, and a
polyoxyethylenated group comprising from 5 to 30 ethylene oxide
units, and ethylenically unsaturated monomers comprising at least
one tertiary amine function.
73. The composition according to claim 72, wherein the alkyl group
of R.sub.6 containing from 1 to 4 carbon atoms is chosen from a
methyl, ethyl, propyl, and isobutyl group.
74. The composition according to claim 72, wherein at least one of
R.sub.6 and R.sub.10 is chosen from 2-hydroxypropyl methacrylate,
2-hydroxyethyl methacrylate, and trifluoroethyl methacrylate.
75. The composition according to claim 72, wherein the alkyl group
of at least one of R.sub.6, R.sub.9, and R.sub.10 is substituted
with halogen atoms chosen from chlorine, bromine, iodine, and
fluorine.
76. The composition according to claim 72, wherein the
(C.sub.1-C.sub.12)alkyl-O-POE of R.sub.10 is methoxy-POE.
77. The composition according to claim 70, wherein the at least one
additional monomer is chosen from acrylic acid, methacrylic acid,
and trifluoroethyl methacrylate.
78. The composition according to claim 70, wherein the at least one
additional monomer is present in an amount ranging from 1% to 30%
by weight relative to the total weight of the at least one first
and/or second blocks of the at least one block polymer.
79. The composition according to claim 1, wherein each of the at
least one first and second blocks comprises at least one monomer
chosen from acrylic acid, acrylic acid esters, methacrylic acid,
and methacrylic acid esters.
80. The composition according to claim 1, wherein each of the at
least one first and second blocks is totally derived from at least
one monomer chosen from acrylic acid, acrylic acid esters,
methacrylic acid, and methacrylic acid esters.
81. The composition according to claim 10, wherein the difference
between the Tg of the at least one first and second blocks is
greater than 10.degree. C.
82. The composition according to claim 81, wherein the difference
between the Tg of the at least one first and second blocks is
greater than 20.degree. C.
83. The composition according to claim 82, wherein the difference
between the Tg of the at least one first and second blocks is
greater than 30.degree. C.
84. The composition according to claim 83, wherein the difference
between the Tg of the at least one first and second blocks is
greater than 40.degree. C.
85. The composition according to claim 10, wherein the at least one
intermediate segment has a Tg between the Tgs of the at least one
first and second blocks.
86. The composition according to claim 1, wherein the at least one
block polymer has a polydispersity index I of greater than 2.0.
87. The composition according to claim 86, wherein the at least one
block polymer has a polydispersity index of greater than or equal
to 2.5.
88. The composition according to claim 87, wherein the at least one
block polymer has a polydispersity index of greater than or equal
to 2.8.
89. The composition according to claim 88, wherein the at least one
block polymer has a polydispersity index ranging from 2.8 to 6.
90. The composition according to claim 1, wherein the at least one
block polymer is a film-forming linear block ethylene polymer.
91. The composition according to claim 1, wherein the at least one
block polymer has a weight-average mass (Mw) which is less than or
equal to 300,000.
92. The composition according to claim 91, wherein the at least one
block polymer has a weight-average mass (Mw) which ranges from
35,000 to 200,000.
93. The composition according to claim 92, wherein the at least one
block polymer has a weight-average mass (Mw) which ranges from
45,000 to 150,000.
94. The composition according to claim 1, wherein the at least one
block polymer has a number-average mass (Mn) which is less than or
equal to 70,000.
95. The composition according to claim 94, wherein the at least one
block polymer has a number-average mass (Mn) which ranges from
10,000 to 60,000.
96. The composition according to claim 95, wherein the at least one
block polymer has a number-average mass (Mn) which ranges from
12,000 to 50,000.
97. The composition according to claim 1, wherein the at least one
block polymer is not soluble to an active material content of at
least 1% by weight in water or in a mixture of water and of a
linear or branched lower monoalcohol having from 2 to 5 carbon
atoms, without pH modification, at room temperature (25.degree.
C.).
98. The composition according to claim 1, wherein the at least one
block polymer is not an elastomer.
99. The composition according to claim 1, wherein the at least one
block polymer is present in an amount ranging from 0.1% to 60% by
weight relative to the total weight of the composition.
100. The composition according to claim 99, wherein the at least
one block polymer is present in an amount ranging from 0.5% to 50%
by weight relative to the total weight of the composition.
101. The composition according to claim 100, wherein the at least
one block polymer is present in an amount ranging from 1% to 40% by
weight relative to the total weight of the composition.
102. The composition according to claim 1, wherein the at least one
organic solvent medium comprises an organic solvent chosen from:
ketones that are liquid at room temperature; alcohols that are
liquid at room temperature; glycols that are liquid at room
temperature; propylene glycol ethers that are liquid at room
temperature; cyclic ethers; short-chain esters containing from 3 to
8 carbon atoms in total; ethers that are liquid at room
temperature; alkanes that are liquid at room temperature; alkyl
sulphoxides; aldehydes that are liquid at room temperature;
heterocyclic compounds; and propylene carbonate or ethyl
3-ethoxypropionate.
103. The composition according to claim 102, wherein the ketones
that are liquid at room temperature are chosen from methyl ethyl
ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone,
cyclohexanone, and acetone.
104. The composition according to claim 102, wherein the alcohols
that are liquid at room temperature are chosen from ethanol,
isopropanol, diacetone alcohol, 2-butoxyethanol, and
cyclohexanol.
105. The composition according to claim 102, wherein the glycols
that are liquid at room temperature are chosen from ethylene
glycol, propylene glycol, pentylene glycol, and glycerol.
106. The composition according to claim 102, wherein the propylene
glycol ethers that are liquid at room temperature are chosen from
propylene glycol monomethyl ether, propylene glycol monomethyl
ether acetate, and dipropylene glycol mono-n-butyl ether.
107. The composition according to claim 102, wherein the cyclic
ethers are chosen from .gamma.-butyrolactones.
108. The composition according to claim 102, wherein the
short-chain esters containing from 3 to 8 carbon atoms in total are
chosen from ethyl acetate, methyl acetate, propyl acetate,
isopropyl acetate, n-butyl acetate, isopentyl acetate,
methoxypropyl acetate, and butyl lactate.
109. The composition according to claim 102, wherein the ethers
that are liquid at room temperature are chosen from diethyl ether,
dimethyl ether, and dichlorodiethyl ether.
110. The composition according to claim 102, wherein the alkanes
that are liquid at room temperature are chosen from decane,
heptane, dodecane, and cyclohexane.
111. The composition according to claim 102, wherein the alkyl
sulphoxides are dimethyl sulphoxides.
112. The composition according to claim 102, wherein the aldehydes
that are liquid at room temperature are chosen from benzaldehyde
and acetaldehyde.
113. The composition according to claim 102, wherein the
heterocyclic compounds are tetrahydrofurans.
114. The composition according to claim 1, wherein the at least one
organic solvent medium has a polarity P ranging from 0.422 to
0.725.
115. The composition according to claim 1, wherein the at least one
organic solvent medium is present in an amount ranging from 10% to
95% by weight relative to the total weight of the composition.
116. The composition according to claim 115, wherein the at least
one organic solvent medium is present in an amount ranging from 15%
to 80% by weight relative to the total weight of the
composition.
117. The composition according to claim 116, wherein the at least
one organic solvent medium is present in an amount ranging from 20%
to 60% by weight relative to the total weight of the
composition.
118. The composition according to claim 1, further comprising at
least one additional film-forming polymer.
119. The composition according to claim 118, wherein the at least
one additional film-forming polymer is present in an amount ranging
from 0.1% to 60% by weight relative to the total weight of the
composition.
120. The composition according to claim 119, wherein the at least
one additional film-forming polymer is present in an amount ranging
from 2% to 40% by weight relative to the total weight of the
composition.
121. The composition according to claim 120, wherein the at least
one additional film-forming polymer is present in an amount ranging
from 5% to 25% by weight relative to the total weight of the
composition.
122. The composition according to claim 1, further comprising at
least one plasticizer present in an amount of less than 20% by
weight relative to the total weight of the composition.
123. The composition according to claim 122, wherein the at least
one plasticizer is present in an amount of less than 15% by weight
relative to the total weight of the composition.
124. The composition according to claim 123, wherein the at least
one plasticizer is present in an amount of less than 10% by weight
relative to the total weight of the composition.
125. The composition according to claim 124, wherein the at least
one plasticizer is present in an amount of less than 5% by weight
relative to the total weight of the composition.
126. The composition according to claim 1, further comprising at
least one dyestuff.
127. The composition according to claim 126, wherein the at least
one dyestuff is present in an amount ranging from 0.01% to 50% by
weight relative to the total weight of the composition.
128. The composition according to claim 127, wherein the at least
one dyestuff is present in an amount ranging from 0.01% to 30% by
weight relative to the total weight of the composition.
129. A non-therapeutic cosmetic makeup or care process for nails,
the process comprising applying to the nails one coat of a nail
varnish composition comprising, in a cosmetically acceptable
medium, at least one block polymer, the composition being capable
of forming a film with a dampening power (tg.delta.) of greater
than or equal to 0.4 at a temperature of 30.degree. C. and a
frequency of 20 Hz.
130. A method for producing a glossy film comprising applying to
nails a nail varnish composition comprising, in a cosmetically
acceptable medium, at least one block polymer, the composition
being capable of forming a film with a dampening power (tg.delta.)
of greater than or equal to 0.4 at a temperature of 30.degree. C.
and a frequency of 20 Hz, wherein a film is produced on the nails
and the film has at least one of good staying power and good wear
resistance.
131. A nail varnish product comprising: i) a container delimiting
at least one compartment closed by a cap, and ii) a composition
received inside said compartment, said composition comprising, in a
cosmetically acceptable medium comprising at least one organic
solvent, at least one block polymer, the composition being capable
of forming a film with a dampening power (tg.delta.) of greater
than or equal to 0.4 at a temperature of 30.degree. C. and a
frequency of 20 Hz.
132. A nail varnish product according to claim 131 wherein the
container is, at least in part, formed of glass.
133. A nail varnish product according to claim 131 wherein the
container is, at least in part, formed of a material other than a
glass.
134. A nail varnish product according to claim 133, wherein said
material other than glass is chosen from thermoplastic materials
and from metals.
135. A nail varnish product according to claim 134, wherein said
thermoplastic materials are chosen from polypropylene and
polyethylene.
136. A nail varnish product according to claim 131, wherein in a
closed position of the container, the cap is linked to the
container by a threading arrangement.
137. A nail varnish product according to claim 131, wherein in a
closed position of the container, the cap is linked to the
container by an arrangement other than a threading arrangement,
such as snap-fitting.
138. A nail varnish product according to claim 131, wherein it
comprises an applicator element in the form of a brush having at
least one tuft of bristles.
139. A nail varnish product according to claim 131, wherein it
comprises an applicator element in a form other than a brush having
at least one tuft of bristles.
140. A nail varnish composition according to claim 139, wherein
said applicator element is in the form of a spatula or a foam pad.
Description
[0001] This application claims priority under 35 U.S.C. .sctn.119
of Application No. 0211949, filed Sep. 26, 2002, Application No.
0216437, filed Dec. 20, 2002, and Application No. 0306121, filed
May 21, 2003, in France, all of which are incorporated herein by
reference.
[0002] The present invention relates to a nail varnish composition
comprising at least one block polymer. The invention also relates
to a makeup or care process for the nails.
[0003] Compositions to be applied, for example to the nails, such
as solvent-based nail varnishes or nailcare bases, usually
comprising at least one film-forming polymer, optionally at least
one plasticizer, pigments, rheological agents and solvents, are
known.
[0004] At the present time, nitrocellulose is the film-forming
agent most widely used in solvent-based nail varnishes in
formulations with optimized gloss and staying power.
[0005] Formulations comprising nitrocelluloses may make it possible
to obtain films with a satisfactory level of hardness and gloss,
but the formulations may lack adhesion to the nail. This drawback
may be overcome by adding plasticizers, but the addition of
plasticizers or co-resins to such formulations generally requires
that they be added in very large amounts, on the order of those of
the nitrocellulose.
[0006] Furthermore, the presence of plasticizers in these
formulations may be reflected, after formation of the film and
drying, by a change in the properties of the film over time. This
may be due both to a slow evaporation of the residual solvents
contained in the film after drying and to a potential loss of some
of the plasticizers, for example by evaporation, leading to
hardening of the film over time and poor chip resistance of the
film.
[0007] The research efforts made towards replacing nitrocellulose
with other film-forming agents, such as polyacrylics and
polyurethanes, in nail varnishes--for instance the aqueous
polyurethane dispersions described in document EP 0 648 485--have
not given completely satisfactory results, for example, in terms of
staying power and resistance to external factors, such as water or
detergents.
[0008] The present inventors have discovered, surprisingly, that a
nail varnish composition with a tangent delta (tg.delta.) dampening
power of greater than or equal to 0.4 makes it possible to obtain
at least one of the following properties, while at the same time
producing a film of glossy composition:
[0009] plasticization of the resulting film without needing to add
large amounts of external plasticizers, while at the same time
maintaining a good level of hardness of the film, and
[0010] good impact strength and/or chip strength of the nail
varnish composition and therefore an improvement in the staying
power of the varnishes on the nail over time and/or in their wear
resistance.
[0011] Disclosed herein is a nail varnish composition comprising,
in a cosmetically acceptable medium comprising at least one organic
solvent, at least one block polymer, the composition being capable
of forming a film with a tangent delta (tg.delta.) dampening power
of greater than or equal to 0.4 at a temperature of 30.degree. C.
and a frequency of 20 Hz.
[0012] As defined herein, the expression "cosmetically acceptable
medium" means a non-toxic medium that may be applied to at least
one of human skin, integuments, and the lips of the face.
[0013] Also disclosed herein is a cosmetic non-therapeutic makeup
or care process for the nails, comprising applying to the nails one
coat of the nail varnish composition as defined above.
[0014] Further disclosed herein is a method for producing a glossy
film comprising applying to nails a nail varnish composition
comprising at least one block polymer, the composition being
capable of forming a film with a tangent delta (tg.delta.)
dampening power of greater than or equal to 0.4 at a temperature of
30.degree. C. and a frequency of 20 Hz, wherein a glossy film is
produced with at least one of good staying power and good wear
resistance.
[0015] The at least one block polymer disclosed herein may be
formulated as a sole film-forming polymer or may be combined with
at least one standard film-forming polymer, for example
nitrocellulose or a cellulose derivative, without having the
drawback, in the case of a cellulose derivative, of adding large
amounts of plasticizers.
[0016] The composition disclosed herein may be capable of forming a
film having viscoelastic behavior.
[0017] In general, a material may be viscoelastic when, due to the
effect of shear, it has both the characteristics of a purely
elastic material, i.e., it is capable of storing energy, and the
characteristics of a purely viscous material, i.e., it is capable
of dissipating energy, and for which the response to stresses is a
function of time (non-instantaneous response).
[0018] The film of the composition disclosed herein may be
characterized by its dampening power tg.delta., which is defined as
the ratio between the dissipated energy and the transmitted energy
in the material.
[0019] The composition disclosed herein may be capable of forming a
film with a dampening power tg.delta. of greater than or equal to
0.4, for example ranging from 0.4 to 1.5, in an embodiment greater
than or equal to 0.5, for example ranging from 0.5 to 1.5, and in
another embodiment greater than or equal to 0.6, for example
ranging from 0.6 to 1, at a temperature of 30.degree. C. and a
frequency of 20 Hz. Moreover, the composition disclosed herein may
be capable of forming a film with a storage modulus E' of greater
than or equal to 1 MPa, for example ranging from 1 MPa to 5000 MPa,
in one embodiment greater than or equal to 5 MPa, for example
ranging from 5 to 1000 MPa, and in another embodiment greater than
or equal to 10 MPa, for example ranging from 10 to 500 MPa, at a
temperature of 30.degree. C. and a frequency of 0.1 Hz.
[0020] Methods for Measuring the Characteristics of the Film
Obtained with the Inventive Composition
[0021] The dampening power tg.delta. is measured by DMTA (Dynamic
and Mechanical Temperature Analysis).
[0022] To measure the dampening power tg.delta. of the film of the
composition, viscoelasticimetry tests are performed using a DMTA
machine from Polymer TA Instruments (model DMA2980) on a sample of
film of the composition. The sample is prepared by pouring the
composition into a Teflon-coated mold, followed by drying on a
plate thermostatically maintained at 30.degree. C. for 24 hours,
under ambient humidity conditions (such as 50%.+-.15% RH).
Specimens are then cut from the film thus obtained (for example
using a sample punch). These specimens may be about 200 .mu.m
thick, about 5 to 10 mm wide and have a working length of about 10
to 15 mm, after drying for 24 hours.
[0023] The measurements are performed at a constant temperature of
30.degree. C.
[0024] The sample is subjected to a tensile stress and small
strains (for example, a sinusoidal displacement of .+-.8 .mu.m is
applied thereto) during frequency scanning, the frequency ranging
from 0.1 to 20 Hz. The process is thus performed in the linear
domain, with small levels of strain.
[0025] From these measurements, the complex modulus E*=E' +iE" of
the film of the test composition may be determined, wherein E' is
the storage modulus and E" is the loss modulus. From these
measurements, the dampening power: tg.delta.=E"/E', is also
deduced.
[0026] The composition disclosed herein may be, for example,
capable of forming a film having a breaking strain of greater than
or equal to 5%, for example ranging from 5% to 500%, and in an
embodiment greater than or equal to 15%, for example ranging from
15% to 400%, and/or a breaking energy per unit volume Wr of greater
than or equal to 0.2 J/cm.sup.3, for example ranging from 0.2 to
100 J/cm.sup.3, and in an embodiment greater than 1 J/cm.sup.3, for
example ranging from 1 to 50 J/cm.sup.3.
[0027] The breaking strain and the breaking energy per unit volume
are determined by tensile tests performed on a film of the
composition about 200 .mu.m thick. The film is obtained by pouring
the composition onto a Teflon-coated mold, followed by drying on a
plate thermostatically maintained at 30.degree. C. for 7 days,
under ambient humidity conditions (such as 50%.+-.15% RH). To
perform these tests, the film is cut into, for example,
dumbbell-shaped specimens with a working length of 33.+-.1 mm and a
working width of 6 mm. The cross section (S) of the specimen is
then defined as: S=width.times.thickness (cm.sup.2); this cross
section will be used to calculate the stress.
[0028] The tests are performed, for example, on a tensile testing
machine sold under the name LLOYD.RTM. LR5K. The measurements are
performed at 20.degree. C.
[0029] The specimens are pulled at a travelling speed of 33
mm/minute, corresponding to a rate of 100% elongation per
minute.
[0030] A travelling speed is thus applied and the elongation
.DELTA.L of the specimen and the force F required to apply this
elongation are simultaneously measured. From these data .DELTA.L
and F, the stress .sigma. and strain .epsilon. parameters are
determined.
[0031] A curve of stress .sigma.=(F/S) as a function of the strain
.epsilon.=(.DELTA.L/Lo).times.100 is thus obtained. The test is
conducted until the specimen breaks, wherein Lo is the initial
length of the specimen.
[0032] The breaking strain is the maximum strain of the sample
before the breaking point (in %).
[0033] The breaking energy per unit volume (Wr) in J/cm.sup.3 is
defined as the area under this stress/strain curve such that: 1 W r
= 0 ??
[0034] 1) Block Polymer
[0035] The at least one block polymer of the composition disclosed
herein may be, for example, a film-forming linear block ethylene
polymer.
[0036] For purposes of the invention, the term "ethylene polymer"
is understood to mean a polymer obtained by the polymerization of
monomers containing an ethylenically unsaturated group.
[0037] The term "block polymer" is understood to mean a polymer
containing at least two separate blocks, for example at least three
separate blocks.
[0038] The block polymer may be a polymer with, for example, a
linear structure. In contrast, a polymer having a non-linear
structure may be, for example, a polymer with a branched, star,
grafted or other structure.
[0039] The term "film-forming polymer" is understood to mean a
polymer capable of forming, by itself or in the presence of at
least one auxiliary film-forming agent, a continuous film that
adheres to a support, for example, to keratinous materials.
[0040] The at least one block polymer of the composition according
to the present invention comprises at least one first block and at
least one second block that have different glass transition
temperatures (Tg). The at least one first and second blocks may be
linked together via at least one intermediate segment comprising at
least one constituent monomer of the at least one first block and
at least one constituent monomer of the at least one second block.
In one embodiment, the at least one first block and the at least
one second block are incompatible with each other.
[0041] The expression blocks "that are incompatible with each
other" means that the mixture of the polymer formed by the at least
one first block and the polymer formed by the at least one second
block (hereinafter referred to as "the polymer mixture") is
immiscible in the main polymerization organic solvent of the block
copolymer at room temperature (25.degree. C.) and atmospheric
pressure (10.sup.5 Pa), at a content of the polymer mixture greater
or equal to 5% by weight of the total weight of polymers and
solvent, and wherein
[0042] (i) the polymer formed by the at least one first block and
the polymer formed by the at least one second block are present in
the polymer mixture in a ratio ranging from 10/90 to 90/10 by
weight, and
[0043] (ii) each of the polymer formed by the at least one first
block and the polymer formed by the at least one second block has
an average molar mass (weight-average or number-average molar mass)
equal to the average mass of the block polymer +/-15%.
[0044] The expression "main polymerization organic solvent" means,
in the case where there is a mixture of polymerization solvents,
the polymerization solvent which has the highest content by weight
relative to the total weight of the organic polymerization
solvents. In the case where there is a mixture of polymerization
solvents and two or more of the solvents are present in identical
weight ratios, the polymer mixture is immiscible in at least one of
the solvents. In the case where the polymerization is made in a
single solvent, the single solvent is the main solvent.
[0045] The at least one intermediate segment may be a block
comprising at least one constituent monomer of the at least one
first block and at least one constituent monomer of the at least
one second block of the polymer and allows these blocks to be
"compatibilized."
[0046] In one embodiment, the at least one block polymer does not
comprise any silicon atoms in its skeleton. The term "skeleton"
means the main chain of the polymer, as opposed to the pendent side
chains.
[0047] In one embodiment, the polymer disclosed herein is not
water-soluble, that is to say the polymer is not soluble in water
or in a mixture of water and linear or branched lower monoalcohols
having from 2 to 5 carbon atoms, such as ethanol, isopropanol, or
n-propanol, without pH modification, with an active material
content of less than 1% by weight, at room temperature (25.degree.
C.).
[0048] In one embodiment, the at least one block polymer is not an
elastomer.
[0049] The expression "non-elastomeric polymer" means a polymer
which, when submitted to a stretching stress (for example when
stretched by 30% of the original length) does not return to
approximately its original length when released. Specifically,
"non-elastomeric polymer" means a polymer with an instantaneous
recovery R.sub.i<50% and a delayed recovery R.sub.2h<70%
after having undergone a 30% elongation. In one embodiment, R.sub.i
is <30% and R.sub.2h is <50%.
[0050] More specifically, the elastomeric nature of the polymer may
be determined according to the following protocol:
[0051] A polymer film is prepared by pouring a solution of the
polymer into a Teflon-coated mold followed by drying for 7 days
under ambient conditions regulated to 23.+-.5.degree. C. and
50.+-.10% relative humidity. A film about 100 .mu.m thick is thus
obtained, from which are cut for example rectangular specimens (for
example using a punch) 15 mm wide and 80 mm long. This sample is
subjected to a tensile stress using a machine sold under the
reference Zwick, under the same temperature and humidity conditions
as for the drying operation. The specimens are drawn at a speed of
50 mm/minute and the distance between the jaws of the machine is 50
mm, which corresponds to the initial length (Lo) of the
specimen.
[0052] The instantaneous recovery R.sub.i is determined in the
following manner:
[0053] The specimen is stretched by 30% (.epsilon..sub.max), i.e.,
about 0.3 times its initial length (Lo). The stress is released by
applying a return speed equal to the tensile speed, i.e., 50
mm/minute, and the residual elongation percentage of the specimen,
after returning to zero stress (.epsilon..sub.i), is measured.
[0054] The percentage instantaneous recovery (R.sub.i) is given by
the formula below:
R.sub.i=((.epsilon..sub.max-.epsilon..sub.i)/.epsilon..sub.max).times.100
[0055] To determine the delayed recovery, the residual percentage
degree of elongation (.epsilon..sub.2h) of the specimen is measured
2 hours after returning to zero stress.
[0056] The delayed percentage recovery in % after 2 hours
(R.sub.2h) is given by the formula below:
R.sub.2h=((.epsilon..sub.max-.epsilon..sub.2h)/.epsilon..sub.max).times.10-
0
[0057] For example, in one embodiment, the at least one block
polymer of the composition disclosed herein has an instantaneous
recovery R.sub.i of 10% and a delayed recovery R.sub.2h of 30%.
[0058] The at least one block polymer disclosed herein comprises at
least one first block and at least one second block that have
different glass transition temperatures (Tg); the at least one
first and second blocks being linked together via at least one
intermediate segment comprising at least one constituent monomer of
the at least one first block and at least one constituent monomer
of the at least one second block.
[0059] It is pointed out that, in the text hereinabove and
hereinbelow, the terms "first" and "second" blocks do not in any
way condition the order of the blocks in the structure of the
polymer.
[0060] The polydispersity index of the polymer disclosed herein may
be greater than 2, for example ranging from 2 to 9, in one
embodiment greater than or equal to 2.5, for example ranging from
2.5 to 8, and in another embodiment greater than or equal to 2.8,
and for example ranging from 2.8 to 6.
[0061] The polydispersity index I of the polymer may be equal to
the ratio of the weight-average mass Mw to the number-average mass
Mn.
[0062] The weight-average (Mw) and number-average (Mn) molar masses
are determined by gel permeation liquid chromatography (THF
solvent, calibration curve established with linear polystyrene
standards, refractometric detector).
[0063] The weight-average mass (Mw) of the polymer disclosed herein
may be, for example, less than or equal to 300,000, for example
ranging from 35,000 to 200,000, and as a further example, ranging
from 45,000 to 150,000.
[0064] The number-average mass (Mn) of the polymer disclosed herein
may be less than or equal to 70,000, for example ranging from
10,000 to 60,000, and as a further example, ranging from 12,000 to
50,000.
[0065] Each block of the at least one block polymer of the
composition disclosed herein may be derived from one type of
monomer or from several different types of monomers.
[0066] This means that each block may comprise a homopolymer or a
copolymer. This copolymer constituting the block may in turn be
random or alternating.
[0067] The at least one intermediate segment comprising at least
one constituent monomer of the at least one first block and at
least one constituent monomer of the at least one second block of
the polymer may be a random polymer.
[0068] In an embodiment, the at least one intermediate segment may
be, for example, derived from constituent monomers of the at least
one first block and of the at least one second block. For example,
the at least one intermediate segment may be at least 85% derived
from constituent monomers of the at least one first block and of
the at least one second block, in a further embodiment at least 90%
derived, for example at least 95%, and as a further example 100%
derived.
[0069] The at least one intermediate segment of the at least one
block polymer has a glass transition temperature Tg ranging from
the glass transition temperatures of the at least one first and
second blocks.
[0070] The at least one first and second blocks of the at least one
block polymer of the composition have different glass transition
temperatures.
[0071] The glass transition temperatures indicated for the at least
one first and second blocks of the at least one block polymer may
be theoretical Tg values determined from the theoretical Tg values
of the constituent monomers of each of the blocks. The theoretical
Tg values may be found in a reference manual, such as, the Polymer
Handbook, 3rd Edition, 1989, John Wiley, which is hereby
incorporated by reference, according to the following relationship,
known as Fox's law: 2 1 / Tg = i ( _ i / Tg i ) ,
[0072] .omega..sub.i being the mass fraction of the monomer i in
the block under consideration and Tg.sub.i being the glass
transition temperature of the homopolymer of the monomer i.
[0073] Unless otherwise indicated, the Tg values indicated for the
at least one first and second blocks of the at least one block
polymer are theoretical Tg values.
[0074] The difference between the glass transition temperatures of
the at least one first and second blocks of the at least one block
polymer may be generally greater than 10.degree. C., for example
greater than 20.degree. C., and as a further example greater than
30.degree. C.
[0075] In one embodiment, the at least one first block of the at
least one block polymer may be chosen from:
[0076] a) a block with a Tg of greater than or equal to 40.degree.
C.,
[0077] b) a block with a Tg of less than or equal to 20.degree. C.,
and
[0078] c) a block with a Tg of between 20 and 40.degree. C.,
[0079] and the at least one second block may be chosen from a block
of category a), b) or c) that is different from the at least one
first block.
[0080] In the present invention, the expression:
[0081] "between . . . and . . . " is intended to denote a range of
values for which the limits mentioned are excluded, and
[0082] "from . . . to . . . " and "ranging from . . . to . . . "
are intended to denote a range of values for which the limits are
included.
[0083] a) Block with a Tq of Greater Than or Equal to 40.degree.
C.
[0084] The block with a Tg of greater than or equal to 40.degree.
C. of the at least one block polymer has, for example, a Tg ranging
from 40 to 150.degree. C., for example greater than or equal to
50.degree. C., for example ranging from 50.degree. C. to
120.degree. C., and as a further example greater than or equal to
60.degree. C., for example ranging from 60.degree. C. to
120.degree. C.
[0085] The block with a Tg of greater than or equal to 40.degree.
C. may be a homopolymer or a copolymer.
[0086] In the case where this block is a homopolymer, it may be
derived from monomers wherein the homopolymers prepared from these
monomers have glass transition temperatures of greater than or
equal to 40.degree. C. This first block may be a homopolymer
comprising one type of monomer (for which the Tg of the
corresponding homopolymer is greater than or equal to 40.degree.
C.).
[0087] In the case where the first block is a copolymer, it may be
totally or partially derived from at least one monomer, the nature
and concentration of which are chosen so that the Tg of the
resulting copolymer is greater than or equal to 40.degree. C. The
copolymer may comprise, for example:
[0088] monomers wherein the homopolymers prepared from these
monomers have Tg values of greater than or equal to 40.degree. C.,
for example a Tg ranging from 40 to 150.degree. C., for example
greater than or equal to 50.degree. C., for example ranging from
50.degree. C. to 120.degree. C., and as a further example greater
than or equal to 60.degree. C., for example ranging from 60.degree.
C. to 120.degree. C., and
[0089] monomers wherein the homopolymers prepared from these
monomers have Tg values of less than 40.degree. C., chosen from
monomers with a Tg of between 20 and 40.degree. C. and/or monomers
with a Tg of less than or equal to 20.degree. C., for example a Tg
ranging from -100 to 20.degree. C., in an embodiment less than
15.degree. C., for example ranging from -80.degree. C. to
15.degree. C., and as a further example less than 10.degree. C.,
for example ranging from -50.degree. C. to 0.degree. C., as
described later.
[0090] The monomers whose homopolymers have a glass transition
temperature of greater than or equal to 40.degree. C. are chosen,
for example, from the following monomers, also known as the main
monomers:
[0091] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1, wherein R.sub.1 is chosen
from linear and branched unsubstituted alkyl groups containing from
1 to 4 carbon atoms, such as methyl, ethyl, propyl and isobutyl
groups, or R.sub.1 is chosen from a C.sub.4 to C.sub.12 cycloalkyl
group,
[0092] acrylates of formula CH.sub.2.dbd.CH--COOR.sub.2, wherein
R.sub.2 is chosen from a C.sub.4 to C.sub.12 cycloalkyl group such
as an isobornyl group or a tert-butyl group,
[0093] (meth)acrylamides of formula: 1
[0094] wherein R.sub.7 and R.sub.8, which may be identical or
different, are chosen from a hydrogen atom, and linear and branched
C.sub.1 to C.sub.12 alkyl groups such as n-butyl, t-butyl,
isopropyl, isohexyl, isooctyl and isononyl groups; or R.sub.7 is H
and R.sub.8 is a 1,1-dimethyl-3-oxobutyl group,
[0095] and R' is chosen from H and methyl. Examples of monomers
that may be mentioned include N-butylacrylamide,
N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide
and N,N-d ibutylacrylamide,
[0096] and mixtures thereof.
[0097] Examples of main monomers are, for example, methyl
methacrylate, isobutyl (meth)acrylate and isobornyl (meth)acrylate,
and mixtures thereof.
[0098] b) Block with a Tq of Less Than or Equal to 20.degree.
C.
[0099] The block with a Tg of less than or equal to 20.degree. C.
of the at least one block polymer has, for example, a Tg ranging
from -100 to 20.degree. C., in an embodiment less than or equal to
15.degree. C., for example ranging from -80.degree. C. to
15.degree. C., and in another embodiment less than or equal to
10.degree. C., for example ranging from -50.degree. C. to 0.degree.
C.
[0100] The block with a Tg of less than or equal to 20.degree. C.
may be a homopolymer or a copolymer.
[0101] In the case where this block is a homopolymer, it may be
derived from monomers wherein the homopolymers prepared from these
monomers have glass transition temperatures of less than or equal
to 20.degree. C. This second block may be a homopolymer comprising
one type of monomer (for which the Tg of the corresponding
homopolymer is less than or equal to 20.degree. C.).
[0102] In the case where the block with a Tg of less than or equal
to 20.degree. C. is a copolymer, it may be totally or partially
derived from at least one monomer, the nature and concentration of
which may be chosen such that the Tg of the resulting copolymer is
less than or equal to 20.degree. C.
[0103] It may comprise, for example,
[0104] at least one monomer whose corresponding homopolymer has a
Tg of less than or equal to 20.degree. C., for example a Tg ranging
from -100.degree. C. to 20.degree. C., in another embodiment less
than 15.degree. C., for example ranging from -80.degree. C. to
15.degree. C., and in another embodiment less than 10.degree. C.,
for example ranging from -50.degree. C. to 0.degree. C., and
[0105] at least one monomer whose corresponding homopolymer has a
Tg of greater than 20.degree. C., such as monomers with a Tg of
greater than or equal to 40.degree. C., for example a Tg ranging
from 40 to 150.degree. C., in another embodiment greater than or
equal to 50.degree. C., for example ranging from 50.degree. C. to
120.degree. C., and in another example greater than or equal to
60.degree. C., for example ranging from 60.degree. C. to
120.degree. C., and/or monomers with a Tg of between 20 and
40.degree. C., as described above.
[0106] In one embodiment, the block with a Tg of less than or equal
to 20.degree. C. is a homopolymer.
[0107] The monomers whose homopolymer has a Tg of less than or
equal to 20.degree. C. may be, for example, chosen from the
following monomers, or main monomer:
[0108] acrylates of formula CH.sub.2.dbd.CHCOOR.sub.3, wherein
R.sub.3 is chosen from linear and branched C.sub.1 to C.sub.12
unsubstituted alkyl groups, with the exception of the tert-butyl
group, wherein at least one heteroatom chosen from O, N and S is
(are) optionally intercalated,
[0109] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.4, wherein R.sub.4 is chosen
from linear and branched C.sub.6 to C.sub.12 unsubstituted alkyl
groups, wherein at least one heteroatom chosen from O, N and S is
(are) optionally intercalated,
[0110] vinyl esters of formula R.sub.5--CO--O--CH.dbd.CH.sub.2,
wherein R.sub.5 is chosen from linear and branched C.sub.4 to
C.sub.12 alkyl groups,
[0111] C.sub.4 to C.sub.12 alcohol and vinyl alcohol ethers,
[0112] N--(C.sub.4 to C.sub.12)alkyl acrylamides, such as
N-octylacrylamide,
[0113] and mixtures thereof.
[0114] Examples of main monomers for the block with a Tg of less
than or equal to 20.degree. C. include, for example, alkyl
acrylates whose alkyl chain contains from 1 to 10 carbon atoms,
with the exception of the tert-butyl group, such as methyl
acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures
thereof.
[0115] c) Block with a Tq of Between 20 and 40.degree. C.
[0116] The block with a Tg of between 20 and 40.degree. C. of the
at least one block polymer may be a homopolymer or a copolymer.
[0117] In the case where this block is a homopolymer, it may be
derived from monomers (or main monomer) wherein the homopolymers
prepared from these monomers have glass transition temperatures of
between 20 and 40.degree. C. This first block may be a homopolymer,
comprising one type of monomer (for which the Tg of the
corresponding homopolymer is between 20.degree. C. to 40.degree.
C.).
[0118] The monomers whose homopolymer has a glass transition
temperature of between 20 and 40.degree. C. may be, for example,
chosen from n-butyl methacrylate, cyclodecyl acrylate, neopentyl
acrylate and isodecylacrylamide, and mixtures thereof.
[0119] In the case where the block with a Tg of between 20 and
40.degree. C. is a copolymer, it may be totally or partially
derived from at least one monomer (or main monomer) whose nature
and concentration are chosen so that the Tg of the resulting
copolymer is between 20 and 40.degree. C.
[0120] The block with a Tg of between 20 and 40.degree. C. may be a
copolymer totally or partially derived from:
[0121] main monomers whose corresponding homopolymer has a Tg of
greater than or equal to 40.degree. C., for example a Tg ranging
from 40.degree. C. to 150.degree. C., in an embodiment greater than
or equal to 50.degree. C., for example ranging from 50 to
120.degree. C., and in another embodiment greater than or equal to
60.degree. C., for example ranging from 60.degree. C. to
120.degree. C., as described above, and/or
[0122] main monomers whose corresponding homopolymer has a Tg of
less than or equal to 20.degree. C., for example a Tg ranging from
-100 to 20.degree. C., in another embodiment less than or equal to
15.degree. C., for example ranging from -80.degree. C. to
15.degree. C., and in another embodiment less than or equal to
10.degree. C., for example ranging from -50.degree. C. to 0.degree.
C., as described above.
[0123] The monomers may be chosen so that the Tg of the copolymer
forming the first block is between 20 and 40.degree. C.
[0124] Such main monomers may be chosen, for example, from methyl
methacrylate, isobornyl acrylate and methacrylate, butyl acrylate
and 2-ethylhexyl acrylate, and mixtures thereof.
[0125] In one embodiment, the proportion of the second block with a
Tg of less than or equal to 20.degree. C. ranges from 10% to 85% by
weight, for example from 20% to 70%, and as a further example from
20% to 50% by weight of the polymer.
[0126] However, each of the blocks of the at least one block
polymer may contain in small proportion at least one constituent
monomer of the other block.
[0127] Thus, the at least one first block of the at least one block
polymer may contain at least one constituent monomer of the at
least one second block, and vice versa.
[0128] Each of the at least one first and/or second blocks of the
at least one block polymer may comprise, in addition to the
monomers indicated above, at least one other monomer known as
additional monomers, which are different from the main monomers
mentioned above.
[0129] The nature and amount of this or these additional monomer(s)
may be chosen such that the block in which they are present has the
desired glass transition temperature.
[0130] This additional monomer may be chosen, for example,
from:
[0131] a) hydrophilic monomers such as:
[0132] ethylenically unsaturated monomers comprising at least one
carboxylic or sulphonic acid function, for example, acrylic acid,
methacrylic acid, crotonic acid, maleic anhydride, itaconic acid,
fumaric acid, maleic acid, acrylamidopropanesulphonic acid,
vinylbenzoic acid, vinylphosphoric acid, and salts thereof,
[0133] ethylenically unsaturated monomers comprising at least one
tertiary amine function, for instance 2-vinylpyridine,
4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl
methacrylate and dimethylaminopropylmethacrylamide, and salts
thereof,
[0134] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6, wherein R.sub.6 is chosen
from linear and branched alkyl groups containing from 1 to 4 carbon
atoms, such as methyl, ethyl, propyl and isobutyl groups, the alkyl
group being substituted with at least one substituent chosen from
hydroxyl groups (for instance 2-hydroxypropyl methacrylate and
2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I or F),
such as trifluoroethyl methacrylate,
[0135] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9, wherein R.sub.9 is chosen
from linear and branched C.sub.6 to C.sub.12 alkyl groups wherein
at least one heteroatom chosen from O, N and S is (are) optionally
intercalated, wherein the alkyl group is substituted with at least
one substituent chosen from hydroxyl groups and halogen atoms (Cl,
Br, I or F);
[0136] acrylates of formula CH.sub.2.dbd.CHCOOR.sub.10, wherein
R.sub.10 may be chosen from linear and branched C.sub.1 to C.sub.12
alkyl groups substituted with at least one substituent chosen from
hydroxyl and halogen atoms (Cl, Br, I or F), such as
2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate;
(C.sub.1-C.sub.1-2)alkyl-O-POE (polyoxyethylene) with repetition of
the oxyethylene unit 5 to 30 times, for example methoxy-POE; and a
polyoxyethylenated group comprising from 5 to 30 ethylene oxide
units
[0137] b) ethylenically unsaturated monomers comprising at least
one silicon atom, such as methacryloxypropyltrimethoxysilane and
methacryloxypropyl-tris(trimethylsiloxy)silane,
[0138] and mixtures thereof.
[0139] Examples of additional monomers include acrylic acid,
methacrylic acid, trifluoroethyl methacrylate, and mixtures
thereof.
[0140] According to an embodiment, the at least one block polymer
of the composition disclosed herein may be a non-silicone polymer,
i.e., a polymer free of silicon atoms.
[0141] This or these additional monomer(s) generally represent(s)
an amount of less than or equal to 30% by weight, for example from
1% to 30% by weight, as a further example from 5% to 20% by weight
and as another example from 7% to 15% by weight, relative to the
total weight of the first and/or second blocks.
[0142] In one embodiment, each of the at least one first and second
blocks of the at least one block polymer comprises at least one
monomer chosen from acrylic acid, acrylic acid esters, methacrylic
acid, methacrylic acid esters, and mixtures thereof.
[0143] In one embodiment, each of the at least one first and second
blocks of the at least one block polymer may be totally derived
from at least one monomer chosen from acrylic acid, acrylic acid
esters, methacrylic acid, and methacrylic acid esters.
[0144] In one embodiment, the block polymer disclosed herein is
free of styrene. "Polymer free of styrene" means that the polymer
contains less than 10% by weight, relative to the total weight of
the polymer, for example, less than 5% by weight, as a further
example less than 2% by weight and as another example less than 1%
by weight, or does not contain at all any styrene monomer including
styrene and styrene derivatives such as for instance methylstyrene,
chlorostyrene or chloromethylstyrene.
[0145] The at least one block polymer of the composition disclosed
herein may be obtained by free-radical solution polymerization
according to the following preparation process:
[0146] a portion of the polymerization solvent is introduced into a
suitable reactor and heated until an adequate temperature for the
polymerization is reached (typically ranging from 60 to 120.degree.
C.),
[0147] once this temperature is reached, the at least one
constituent monomer of the at least one first block is introduced
in the presence of some of the polymerization initiator,
[0148] after a time T corresponding to a maximum degree of
conversion of 90%, the at least one constituent monomer of the at
least one second block and the rest of the initiator are
introduced,
[0149] the mixture is left to react for a time T' (ranging from 3
to 6 hours), after which the mixture is cooled to room temperature
(25.degree. C.),
[0150] the polymer dissolved in the polymerization solvent is
obtained.
[0151] The term "polymerization solvent" means a solvent or a
mixture of solvents. The polymerization solvent may be chosen, for
example, from ethyl acetate, butyl acetate, alcohols such as
isopropanol or ethanol, aliphatic alkanes such as isododecane, and
mixtures thereof. In one embodiment, the polymerization solvent is
a mixture of butyl acetate and isopropanol or isododecane.
[0152] First Embodiment
[0153] According to a first embodiment, the at least one block
polymer of the composition disclosed herein comprises at least one
(for example, one) first block with a Tg of greater than or equal
to 40.degree. C., as described above in a), and at least one (for
example, one) second block with a Tg of less than or equal to
20.degree. C., as described above in b).
[0154] The first block with a Tg of greater than or equal to
40.degree. C. of the at least one block polymer may be a copolymer
derived from monomers wherein the homopolymer prepared from these
monomers has a glass transition temperature of greater than or
equal to 40.degree. C., such as the monomers described above.
[0155] The second block with a Tg of less than or equal to
20.degree. C. may be a homopolymer derived from monomers wherein
the homopolymer prepared from these monomers has a glass transition
temperature of less than or equal to 20.degree. C., such as the
monomers described above.
[0156] The proportion of the block with a Tg of greater than or
equal to 40.degree. C. of the at least one block polymer ranges
from 20% to 90%, for example from 30% to 80%, and as a further
example from 50% to 70% by weight of the polymer. In one
embodiment, the proportion of the block with a Tg of less than or
equal to 20.degree. C. ranges from 5% to 75%, for example from 15%
to 50%, and as a further example from 25% to 45% by weight of the
polymer.
[0157] Thus, according to a first variant, the at least one block
polymer of the composition disclosed herein may comprise:
[0158] at least one first block with a Tg of greater than or equal
to 40.degree. C., for example having a Tg ranging from 70 to
110.degree. C., which is a methyl methacrylate/acrylic acid
copolymer,
[0159] at least one second block with a Tg of less than or equal to
20.degree. C., for example ranging from 0 to 20.degree. C., which
is a methyl acrylate homopolymer, and
[0160] at least one intermediate segment which is a methyl
methacrylate/acrylic acid/methyl acrylate copolymer.
[0161] According to a second variant, the at least one block
polymer of the composition disclosed herein may comprise:
[0162] at least one first block with a Tg of greater than or equal
to 40.degree. C., for example ranging from 70 to 100.degree. C.,
which is a methyl methacrylate/acrylic acid/trifluoroethyl
methacrylate copolymer,
[0163] at least one second block with a Tg of less than or equal to
20.degree. C., for example ranging from 0 to 20.degree. C., which
is a methyl acrylate homopolymer, and
[0164] at least one intermediate segment which is a methyl
methacrylate/acrylic acid/methyl acrylate/trifluoroethyl
methacrylate random copolymer.
[0165] Second Embodiment
[0166] According to a second embodiment, the at least one block
polymer of the composition disclosed herein comprises at least one
first block having a glass transition temperature (Tg) of between
20 and 40.degree. C., in accordance with the blocks described in
c), and at least one second block having a glass transition
temperature of less than or equal to 20.degree. C., as described
above in b), or a glass transition temperature of greater than or
equal to 40.degree. C., as described in a) above.
[0167] The proportion of the at least one first block with a Tg of
between 20 and 40.degree. C. ranges from 10% to 85% by weight of
the polymer, for example from 30% to 80%, and as a further example
from 50% to 70%.
[0168] When the at least one second block is a block with a Tg of
greater than or equal to 40.degree. C., it may be, for example,
present in an amount ranging from 10% to 85% by weight, for example
from 20% to 70%, and as a further example from 30% to 70% by weight
of the polymer.
[0169] When the at least one second block is a block with a Tg of
less than or equal to 20.degree. C., it may be, for example,
present in an amount ranging from 10% to 85% by weight, for example
from 20% to 70%, and as a further example from 20% to 50% by weight
of the polymer.
[0170] The at least one first block with a Tg of between 20 and
40.degree. C. of the at least one block polymer may be a copolymer
derived from monomers wherein the corresponding homopolymer has a
Tg of greater than or equal to 40.degree. C., and from monomers
wherein the corresponding homopolymer has a Tg of less than or
equal to 20.degree. C.
[0171] The at least one second block with a Tg of less than or
equal to 20.degree. C. or with a Tg of greater than or equal to
40.degree. C. may be a homopolymer.
[0172] The at least one block polymer of the composition disclosed
herein comprises:
[0173] at least one first block with a Tg of between 20 and
40.degree. C., for example with a Tg of 25 to 39.degree. C., which
may be a copolymer comprising at least one methyl acrylate monomer,
at least one methyl methacrylate monomer and at least one acrylic
acid monomer,
[0174] at least one second block with a Tg of greater than or equal
to 40.degree. C., for example ranging from 85 to 125.degree. C.,
which may be a homopolymer composed of methyl methacrylate
monomers, and
[0175] at least one intermediate segment comprising at least one
methyl acrylate, methyl methacrylate monomer, and
[0176] at least one intermediate segment comprising methyl
methacrylate, at least one acrylic acid monomer, and at least one
methyl acrylate monomer.
[0177] The composition disclosed herein, for example, comprises
from 0.1% to 60% by weight, for example from 0.5% to 50% by weight,
and as a further example from 1% to 40% by weight, of the at least
one block polymer relative to the total weight of the
composition.
[0178] Solvent Medium
[0179] The cosmetic composition disclosed herein comprises an
organic solvent medium comprising at least one organic solvent.
[0180] The at least one organic solvent may be chosen from:
[0181] ketones that are liquid at room temperature, such as methyl
ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,
isophorone, cyclohexanone, or acetone;
[0182] alcohols that are liquid at room temperature, such as
ethanol, isopropanol, diacetone alcohol, 2-butoxyethanol, or
cyclohexanol;
[0183] glycols that are liquid at room temperature, such as
ethylene glycol, propylene glycol, pentylene glycol, or
glycerol;
[0184] propylene glycol ethers that are liquid at room temperature
such as propylene glycol monomethyl ether, propylene glycol
monomethyl ether acetate, or dipropylene glycol mono-n-butyl
ether;
[0185] cyclic ethers such as .gamma.-butyrolactone;
[0186] short-chain esters (containing from 3 to 8 carbon atoms in
total) such as ethyl acetate, methyl acetate, propyl acetate,
isopropyl acetate, n-butyl acetate, isopentyl acetate,
methoxypropyl acetate, or butyl lactate;
[0187] ethers that are liquid at room temperature, such as diethyl
ether, dimethyl ether, or dichlorodiethyl ether;
[0188] alkanes that are liquid at room temperature, such as decane,
heptane, dodecane, or cyclohexane;
[0189] alkyl sulphoxides, such as dimethyl sulphoxide;
[0190] aldehydes that are liquid at room temperature, such as
benzaldehyde or acetaldehyde;
[0191] heterocyclic compounds such as tetrahydrofuran;
[0192] propylene carbonate or ethyl 3-ethoxypropionate; and
[0193] mixtures thereof.
[0194] The solvent may be, for example, chosen from short-chain
esters containing from 3 to 8 carbon atoms in total, such as ethyl
acetate, methyl acetate, propyl acetate, isopropyl acetate, n-butyl
acetate, isopentyl acetate, methoxypropyl acetate, or butyl
lactate, and mixtures thereof.
[0195] The organic solvent medium, for example, has a polarity P
ranging from 0.422 to 0.725.
[0196] The polarity is defined as a function of the solubility
parameters according to the Hansen solubility space, according to
the following relationship:
P={square root}(.delta.p.sup.2+.delta.h.sup.2)/.delta.t
[0197] .delta.h defines the specific forces of interaction (such as
hydrogen bonding, acid/base bonding, donor/acceptor bonding,
etc.);
[0198] .delta.p defines the Debye interaction forces between
permanent dipoles and also the Keesom interaction forces between
induced dipoles and permanent dipoles; and
[0199] .delta.t={square
root}(.delta.p.sup.2+.delta.h.sup.2+.delta.d.sup.2- ), .delta.d
defines the London dispersion forces derived from the formation of
induced dipoles during molecular impacts.
[0200] The definition and calculation of the solubility parameters
in the Hansen three-dimensional solubility space are described in
the article by C. M. Hansen, "The three dimensional solubility
parameters," J. Paint Technol., 39, 105 (1967), which is hereby
incorporated by reference.
[0201] When the solvent medium comprises a mixture of solvents, the
polarity may be determined from the solubility parameters of the
mixture, which are themselves determined from those of the
compounds taken separately, according to the following
relationships:
.delta.dmixt=.SIGMA.xi.delta.di; .delta.pmixt=.SIGMA.xi.delta.pi
and .delta.hmixt=.SIGMA.xi.delta.hi
[0202] i i i
[0203] wherein xi is the volume fraction of the compound i in the
mixture.
[0204] As organic solvents with a polarity ranging from 0.422 to
0.725, mention may be made, for example, of methyl acetate, ethyl
acetate, isopropyl acetate, methoxypropyl acetate, butyl lactate,
acetone, methyl ethyl ketone, diacetone alcohol,
.gamma.-butyrolactone, tetrahydrofuran, propylene carbonate, ethyl
3-ethoxypropionate and dimethyl sulphoxide, and mixtures
thereof.
[0205] The organic solvent medium may represent from 10% to 95% by
weight, for example from 15% to 80% by weight, and as a further
example from 20% to 60% by weight, relative to the total weight of
the composition.
[0206] Alternatively, the composition disclosed herein may, in one
embodiment, comprise an aqueous medium.
[0207] Additional Film-Forming Polymer
[0208] The composition may comprise, besides the at least one block
polymer of the composition disclosed herein, at least one
additional polymer, for example, a film-forming polymer. According
to the present invention, the term "film-forming polymer" means a
polymer that is capable, by itself or in the presence of at least
one auxiliary film-forming agent, of forming a continuous film that
adheres to a support, for example to keratin materials.
[0209] Among the film-forming polymers that may be used in the
composition of the present invention, mention may be made of
synthetic polymers, of free-radical type or of polycondensate type,
and polymers of natural origin, and mixtures thereof.
[0210] The film-forming polymer may be chosen, for example, from
cellulose-based polymers such as nitrocellulose, cellulose acetate,
cellulose acetobutyrate, cellulose acetopropionate or
ethylcellulose, or alternatively polyurethanes, acrylic polymers,
vinyl polymers, polyvinylbutyrals, alkyd resins, resins derived
from aldehyde condensation products such as
arylsulphonamide-formaldehyde resins, for instance
toluenesulphonamide-formaldehyde resin, and arylsulphonamide-epoxy
resins.
[0211] Film-forming polymers that may be, for example, used include
nitrocellulose RS 1/8 sec.; RS 1/4 sec.; 1/2 sec.; RS 5 sec.; RS 15
sec.; RS 35 sec.; RS 75 sec.; RS 150 sec.; AS 1/4 sec.; AS 1/2
sec.; SS 1/4 sec.; SS 1/2 sec.; SS 5 sec., sold by the company
Hercules; the toluenesulphonamide-formaldehyde resins "KETJENTFLEX
MS80" from the company Akzo or "SANTOLITE MHP" or "SANTOLITE MS 80"
from the company Faconnier or "RESIMPOL 80" from the company Pan
Americana, the alkyd resin "BECKOSOL ODE 230-70-E" from the company
Dainippon, the acrylic resin "ACRYLOID B66" from the company Rohm
& Haas, and the polyurethane resin "TRIXENE PR 4127" from the
company Baxenden.
[0212] The at least one additional film-forming polymer may be
present in the composition disclosed herein in an amount ranging
from 0.1% to 60% by weight, for example ranging from 2% to 40% by
weight, and as a further example from 5% to 25% by weight, relative
to the total weight of the composition.
[0213] Plasticizer
[0214] The composition may also comprise at least one plasticizer.
In particular, mention may be made, alone or as a mixture, of the
usual plasticizers, such as:
[0215] glycols and derivatives thereof chosen from diethylene
glycol ethyl ether, diethylene glycol methyl ether, diethylene
glycol butyl ether or diethylene glycol hexyl ether, ethylene
glycol ethyl ether, ethylene glycol butyl ether, and ethylene
glycol hexyl ether;
[0216] glycerol esters,
[0217] propylene glycol derivatives and for example propylene
glycol phenyl ether, propylene glycol diacetate, dipropylene glycol
butyl ether, tripropylene glycol butyl ether, propylene glycol
methyl ether, dipropylene glycol ethyl ether, tripropylene glycol
methyl ether, diethylene glycol methyl ether and propylene glycol
butyl ether,
[0218] acid esters, for example carboxylic acid esters, chosen from
citrates, phthalates, adipates, carbonates, tartrates, phosphates,
and sebacates,
[0219] oxyethylenated derivatives chosen from oxyethylenated oils,
for example, plant oils chosen from castor oil; and
[0220] mixtures thereof.
[0221] The amount of plasticizer may be chosen by a person skilled
in the art on the basis of his general knowledge, so as to obtain a
composition with cosmetically acceptable properties. The
plasticizer may be, for example, present in an amount of less than
20%, for example less than 15%, as a further example less than 10%,
and as an additional example less than 5% by weight relative to the
total weight of the composition. In one embodiment, the composition
disclosed herein is free of plasticizer.
[0222] Dyestuff
[0223] The composition disclosed herein may also comprise at least
one dyestuff chosen from water-soluble dyes and pulverulent
dyestuffs, for instance pigments, nacres and flakes that are well
known to those skilled in the art. The dyestuffs may be present in
the composition in an amount ranging from 0.01% to 50% by weight
and for example from 0.01% to 30% by weight relative to the weight
of the composition.
[0224] The term "pigments" should be understood as meaning white or
colored, mineral or organic particles of any shape, which are
insoluble in the physiological medium and which are intended to
color the composition.
[0225] The term "nacres" should be understood as meaning iridescent
particles of any shape, produced for example by certain molluscs in
their shell, or alternatively synthesized.
[0226] The pigments may be white or colored, and mineral and/or
organic. Among the mineral pigments that may be mentioned are
titanium dioxide, optionally surface-treated, zirconium oxide or
cerium oxide, and also zinc oxide, iron oxide (black, yellow or
red) or chromium oxide, manganese violet, ultramarine blue,
chromium hydrate and ferric blue, and metal powders, for instance
aluminium powder or copper powder. Among the organic pigments that
may be mentioned are carbon black, pigments of D & C type, and
lakes based on cochineal carmine or on barium, strontium, calcium
or aluminium.
[0227] The nacreous pigments may be chosen from white nacreous
pigments such as mica coated with titanium or with bismuth
oxychloride, coloured nacreous pigments such as titanium mica
coated with iron oxides, titanium mica coated for example with
ferric blue or chromium oxide, titanium mica coated with an organic
pigment of the above-mentioned type and also nacreous pigments
based on bismuth oxychloride.
[0228] The water-soluble dyes are, for example, beetroot juice or
methylene blue.
[0229] The composition disclosed herein may also comprise at least
one filler, for example in an amount ranging from 0.01% to 50% by
weight and for example ranging from 0.01% to 30% by weight,
relative to the total weight of the composition. The term "filler"
should be understood as meaning colorless or white, mineral or
synthetic particles of any shape, which are insoluble in the medium
of the composition, irrespective of the temperature at which the
composition is manufactured. These fillers serve for example to
modify the rheology or the texture of the composition.
[0230] The at least one filler may be mineral or organic in any
form, platelet-shaped, spherical or oblong, irrespective of the
crystallographic form (for example leaflet, cubic, hexagonal,
orthorhombic, etc.). Mention may be made of talc, mica, silica,
kaolin, polyamide (NYLON.RTM.) powders (ORGASOL.RTM. from Atochem),
poly-.beta.-alanine powder and polyethylene powder, powders of
polytetrafluoroethylene polymers (TEFLON.RTM.), lauroyllysine,
starch, boron nitride, hollow polymer microspheres such as those of
polyvinylidene chloride/acrylonitrile, for instance EXAPANCEL.RTM.
(Nobel Industrie) or acrylic acid copolymers (POLYTRAP.RTM. from
the company Dow Corning) and silicone resin microbeads (for example
TOSPEARLS.RTM. from Toshiba), elastomeric polyorganosiloxane
particles, precipitated calcium carbonate, magnesium carbonate,
magnesium hydrocarbonate, hydroxyapatite, hollow silica
microspheres (SILICA BEADS.RTM. from Maprecos), glass or ceramic
microcapsules, and metal soaps derived from organic carboxylic
acids containing from 8 to 22 carbon atoms and for example from 12
to 18 carbon atoms, for example zinc, magnesium or lithium
stearate, zinc laurate or magnesium myristate.
[0231] Other Additives
[0232] The composition may also comprise other ingredients commonly
used in cosmetic compositions. Such ingredients may be chosen from
spreading agents, wetting agents, dispersants, antifoams,
preserving agents, UV-screening agents, active agents, surfactants,
moisturizers, fragrances, neutralizers, stabilizers, and
antioxidants.
[0233] Needless to say, a person skilled in the art will take care
to select this or these optional additional compound(s), and/or the
amount thereof, such that the advantageous properties of the
composition disclosed herein are not, or are not substantially,
adversely affected by the envisaged addition.
[0234] The examples that follow illustrate the invention, in a
non-limiting manner.
[0235] In the examples that follow, the Tg values indicated for the
at least one first and second blocks are theoretical Tg values
calculated in the manner defined above.
EXAMPLE 1
Preparation of a poly(methyl methacrylate)/acrylic acid/methyl
Acrylate) Polymer
[0236] 100 g of butyl acetate were introduced into a 1 liter
reactor and the temperature was then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. in 1 hour. 180 g of
methyl methacrylate, 30 g of acrylic acid, 40 g of butyl acetate,
70 g of isopropanol and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX.RTM.
141 from Akzo Nobel) were then added, at 90.degree. C. and over 1
hour.
[0237] The mixture was maintained at 90.degree. C. for 1 hour.
[0238] 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0239] The mixture was maintained at 90.degree. C. for 3 hours and
then diluted with 105 g of butyl acetate and 45 g of isopropanol,
and the mixture was then cooled.
[0240] A solution containing 40% polymer active material in a butyl
acetate/isopropanol mixture was obtained.
[0241] A polymer comprising a poly(methyl methacrylate/acrylic
acid) first block with a Tg of 100.degree. C., a polymethyl
acrylate second block with a Tg of 10.degree. C. and an
intermediate segment which was a methyl methacrylate/acrylic
acid/polymethyl acrylate random polymer was obtained.
[0242] This polymer had a weight-average mass of 52,000 and a
number-average mass of 18,000, i.e., a polydispersity index I of
2.89.
[0243] It had a storage modulus E' equal to 90 MPa at 30.degree. C.
and 0.1 Hz and a tg.delta. value of 0.33 at 30.degree. C. and 20
Hz.
EXAMPLE 2
Preparation of a poly(methyl methacrylate)/acrylic acid/methyl
Acrylate) Polymer
[0244] 100 g of butyl acetate were introduced into a 1 liter
reactor and the temperature was then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. in 1 hour. 150 g of
methyl methacrylate, 30 g of acrylic acid, 30 g of methyl acrylate,
40 g of butyl acetate, 70 g of isopropanol and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethyl- hexane (TRIGONOX.RTM.
141 from Akzo Nobel) were then added, at 90.degree. C. and over 1
hour.
[0245] The mixture was maintained at 90.degree. C. for 1 hour.
[0246] 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0247] The mixture was maintained at 90.degree. C. for 3 hours and
then diluted with 105 g of butyl acetate and 45 g of isopropanol,
and the mixture was then cooled.
[0248] A solution containing 40% polymer active material in a butyl
acetate/isopropanol mixture was obtained.
[0249] A polymer comprising a poly(acrylic acid/methyl acrylate)
first block with a Tg of 80.degree. C., a polymethyl acrylate
second block with a Tg of 10.degree. C. and an intermediate segment
which was an acrylic acid/methyl acrylate/polymethyl acrylate
random polymer was obtained.
[0250] This polymer had a weight-average mass of 50,000 and a
number-average mass of 17,000, i.e., a polydispersity index I of
2.95.
[0251] It had a storage modulus E' equal to 12 MPa at 30.degree. C.
and 0.1 Hz and a tg.delta. value of 0.54 at 30.degree. C. and 20
Hz.
EXAMPLE 3
Preparation of a Poly(acrylic Acid/methyl Acrylate/methyl
Acrylate/trifluoroethyl Methacrylate) Polymer
[0252] 100 g of butyl acetate were introduced into a 1 litre
reactor and the temperature was then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. in 1 hour. 120 g of
methyl methacrylate, 30 g of acrylic acid, 60 g of trifluoroethyl
methacrylate, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g
of 2,5-bis(2-ethyl-hexanoylperoxy)- -2,5-dimethylhexane
(TRIGONOX.RTM. 141 from Akzo Nobel) were then added, at 90.degree.
C. and over 1 hour.
[0253] The mixture was maintained at 90.degree. C. for 1 hour.
[0254] 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0255] The mixture was maintained at 90.degree. C. for 3 hours and
then diluted with 105 g of butyl acetate and 45 g of isopropanol,
and the mixture was then cooled.
[0256] A solution containing 40% polymer active material in a butyl
acetate/isopropanol mixture was obtained.
[0257] A polymer comprising a poly(acrylic acid/methyl
methacrylate/trifluoroethyl methacrylate) first block with a Tg of
85.degree. C., a polymethyl acrylate second block with a Tg of
10.degree. C. and an intermediate segment which was an acrylic
acid/methyl acrylate/polymethyl acrylate/trifluoroethyl
methacrylate random polymer was obtained.
[0258] This polymer had a weight-average mass of 53,000 and a
number-average mass of 17500, i.e., a polydispersity index I of
3.03.
[0259] It had a storage modulus E' equal to 3 MPa at 30.degree. C.
and 0.1 Hz and a tg.delta. value of 0.34 at 30.degree. C. and 20
Hz.
EXAMPLE 4
Preparation of a Poly(Methyl Methacrylate/methyl Acrylate/acrylic
Acid) Polymer
[0260] 210 g of ethyl acetate were introduced into a 1 litre
reactor and the temperature was then increased so as to pass from
room temperature (25.degree. C.) to 78.degree. C. over 1 hour. 54 g
of methyl methacrylate, 21 g of acrylic acid, 135 g of methyl
acrylate and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX.RTM.
141 from Akzo Nobel) were then added, at 78.degree. C. and over 1
hour.
[0261] The mixture was maintained at 90.degree. C. for 1 hour.
[0262] 90 g of methyl methacrylate, 90 g of ethyl acetate and 1.2 g
of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then
introduced into the above mixture, still at 78.degree. C. and over
1 hour.
[0263] The mixture was maintained at 78.degree. C. for 3 hours and
was then diluted with 150 g of ethyl acetate and cooled.
[0264] A solution containing 40% polymer active material in ethyl
acetate was obtained.
[0265] The polymer obtained comprises a poly(methyl acrylate/methyl
methacrylate/acrylic acid) first block with a Tg of 35.degree. C.,
a poly(methyl methacrylate) second block with a Tg of 100.degree.
C. and an intermediate segment which was a methyl
methacrylate/acrylic acid/polymethyl acrylate random polymer.
[0266] This polymer had a weight-average mass of 141,000 and a
number-average mass of 50,000, i.e., a polydispersity index I of
2.82.
EXAMPLE 5
Preparation of a Poly(Methyl Methacrylate/methyl Acrylate/acrylic
Acid) Polymer
[0267] 100 g of butyl acetate were introduced into a 1 litre
reactor and the temperature was then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour. 50.4 g of
methyl methacrylate, 21 g of acrylic acid, 138.6 g of methyl
acrylate, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of
2,5-bis(2-ethylhexanoylpe- roxy)-2,5-dimethylhexane (TRIGONOX.RTM.
141 from Akzo Nobel) were then added, at 90.degree. C. and over 1
hour.
[0268] The mixture was maintained at 90.degree. C. for 1 hour.
[0269] 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexan- e were then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0270] The mixture was maintained at 90.degree. C. for 3 hours and
then diluted with 105 g of butyl acetate and 45 g of isopropanol,
and cooled.
[0271] A solution containing 40% polymer active material in a butyl
acetate/isopropanol mixture was obtained.
[0272] The polymer obtained comprises a poly(methyl acrylate/methyl
methacrylate/acrylic acid) first block with a Tg of 35.degree. C.,
a poly(methyl methacrylate) second block with a Tg of 100.degree.
C. and an intermediate segment which was a methyl
methacrylate/acrylic acid/polymethyl acrylate random polymer.
EXAMPLE 6
Nail Varnish
[0273] A nail varnish having the composition below was
prepared:
1 Polymer of Example 1 23.8 g AM Butyl acetate 24.99 g Isopropanol
10.71 g Hexyleneglycol 2.5 g DC Red 7 Lake 1 g Hectorite modified
with stearyldimethylbenzylammonium 1.3 g chloride (BENTONE .RTM.
27V from Elementis) Ethyl acetate qs 100 g
[0274] After application to the nails, this varnish was considered
as having very good staying power and impact strength
properties.
EXAMPLE 7
Nail Varnish
[0275] A nail varnish having the composition below may be
prepared:
2 Polymer of Example 4 23.8 g AM Butyl acetate 24.99 g Isopropanol
10.71 g DC Red 7 Lake 1 g Hectorite modified with 1.3 g
stearyldimethylbenzylammonium chloride (BENTONE .RTM. 27V from
Elementis) Ethyl acetate qs 100 g
[0276] Packaging:
[0277] According to another aspect of the invention, there is
provided a nail varnish product comprising: i) a container
delimiting at least one compartment closed by a cap, and ii) a
composition according to the invention received inside the
compartment.
[0278] The container may be in the form of a bottle and can be
formed, at least in part, of glass or of a material other than
glass, such as at least one thermoplastic material, for example at
least one thermoplastic material chosen from polypropylene and
polyethylene, or a metal.
[0279] In a closed position of the container, the cap may be linked
to the container by a threading arrangement.
[0280] As an alternative, the cap may linked to the container by an
arrangement other than a threading arrangement, such as
snap-fitting.
[0281] In one embodiment, the product comprises an applicator
element which can be in the form of a brush having at least one
tuft of bristles. As an alternative, the applicator element may be
in a form other than a brush having at least one tuft of bristles,
for example, in the form of a spatula or a foam pad.
* * * * *